Oil-In-Water Emulsion Type Sunscreen Preparation

ABSTRACT

The object of the present invention is to provide an oil-in-water emulsified sunscreen cosmetic that is superior in stability and the sensation during use. This object is achieved by providing an oil-in-water emulsified sunscreen cosmetic that satisfies all of the following conditions (A), (B), (C), (D), and (E): 
     (A) Containing the following three types of surfactants (A-1)-(A-3) in the amount of 1-6 wt % of the total amount of the cosmetic
         (A-1) A POE stearic ester having a POE mole number of 20-120   (A-2) Sorbitan tristearate   (A-3) Glyceryl stearate having a HLB of 5-8
 
(B) Containing the following oil soluble ultraviolet absorbent, which is solid at room temperature, in the amount of 0.01-5 wt % of the total amount of the cosmetic
   Bis-ethylhexyloxyphenolmethoxyphenyltriazine and/or tert-butylmethoxybenzoylmethane
 
(C) Containing the following oil soluble ultraviolet absorbent, which is liquid at room temperature, in the amount of 1-14 wt % of the total amount of the cosmetic
   Ethylhexyl methoxycinnamate and/or octocrylene
 
(D) Containing the following water soluble ultraviolet absorbent in the amount of 0.1-5 wt % of the total amount of the cosmetic
   Phenylbenzimidazolesulfonic acid
 
(E) Containing higher alcohol having 14-24 carbon atoms

TECHNICAL FIELD

The present invention relates to a sunscreen cosmetic. Morespecifically, it relates to an oil-in-water emulsified sunscreencosmetic that is superior in ultraviolet protection as well as instability and the sensation during use.

BACKGROUND ART

In the field of sunscreen cosmetics, efforts are being made to improvethe sensation during use and stability of the base agent whileincreasing the ultraviolet protection.

For example, Patent Document 1 discloses an oil-in-water emulsifiedsunscreen cosmetic comprising (a) a phospholipid, (b) a non-ionicsurfactant and/or anionic surfactant, (c) an oil soluble ultravioletabsorbent, (d) water, (e) a microbial polysaccharide, (f) sterin, and(g) a water soluble ultraviolet absorbent, said sunscreen cosmetichaving a low viscosity, showing no separation or increased viscosityover time, indicating superior stability, and giving refreshing andmoist tactile sensations.

Patent Citation 1: Japanese Patent Laid-Open 2005-255669 bulletin

DISCLOSURE OF INVENTION Technical Problem

When the ultraviolet absorbent content is increased in order to increasethe ultraviolet protection, usability and the stability of the baseagent become poor. Therefore, the market has long been desiring toimprove usability and the stability of the base agent while increasingthe ultraviolet protection at the same time, and this has been a veryimportant issue for those skilled in the art.

The inventors addressed this important issue and conducted earnestresearch, and, to our surprise, discovered that an oil-in-wateremulsified composition having a specific composition including aspecific surfactant, ultraviolet absorbent, and other ingredientsfunctions as a sunscreen cosmetic that increases the ultravioletprotection and at the same time improve the sensation during use and thestability of the base agent, thus completing the present invention.

In addition, in the present invention it was also discovered that, evenwhen β-alanyl-L-histidine and/or its salt (trivial name: carnosine) wasadded, an increase in the pH of the base agent due to carnosine, whichwas a basic dipeptide, could be prevented.

Technical Solution

That is, the present invention provides a oil-in-water emulsifiedsunscreen cosmetic that satisfies all of the following conditions (A),(B), (C), (D), and (E):

(A) Containing the following three types of surfactants (A-1)-(A-3) inthe amount of 1-6 wt % of the total amount of the cosmetic

(A-1) A POE stearic ester having a POE mole number of 20-120

(A-2) Sorbitan tristearate

(A-3) Glyceryl stearate having a HLB of 5-8

(B) Containing the following oil soluble ultraviolet absorbent, which issolid at room temperature, in the amount of 0.01-5 wt % of the totalamount of the cosmetic

Bis-ethylhexyloxyphenolmethoxyphenyltriazine and/ortert-butylmethoxybenzoylmethane

(C) Containing the following oil soluble ultraviolet absorbent that isliquid at room temperature, in the amount of 1-14 wt % of the totalamount of the cosmetic

Ethylhexyl methoxycinnamate and/or octocrylene

(D) Containing the following water soluble ultraviolet absorbent in theamount of 0.1-5 wt % of the total amount of the cosmetic

Phenylbenzimidazolesulfonic acid or its salt

(E) Containing a higher alcohol having 14-24 carbon atoms

Also, the present invention provides the aforementioned oil-in-wateremulsified sunscreen cosmetic that satisfies the following conditions(1) and (2):

(1) The ingredient (A-3) content is 10-75 wt % of the total amount ofingredients (A-1), (A-2), and (A-3).(2) The ingredient (E) content is 30-90 wt % of the total amount ofingredients (A-1), (A-2), and (A-3).

Furthermore, the present invention provides the aforementionedoil-in-water emulsified sunscreen cosmetic (F) further containing amonoester oil represented by the following formula (1) in the amount of0.2-9 wt % of the total amount of the cosmetic.

[Chemical formula 1]

R₁COOR₂  (1)

(In this formula, R₁ denotes an alkyl group having 5-11 carbon atoms,and R₂ denotes an alkyl group having 3-11 carbon atoms.)

Furthermore, the present invention provides the aforementionedoil-in-water emulsified sunscreen cosmetic (G) further containing arandom copolymer ether compound of ethylene glycol and propylene glycolrepresented by the following formula (2) in the amount of 0.2-9 wt % ofthe total amount of the cosmetic.

[Chemical formula 2]

RO-[(EO)_(m)(AO)_(n)]-OR  (2)

(In this formula, AO denotes an oxyalkylene group having 3-4 carbonatoms, EO denotes an oxyethylene group, m and n, respectively, areaverage addition mole numbers of said oxyalkylene group and oxyethylenegroup; also 1=<m=<70 and 1=<n=<70. The ratio of the oxyethylene group tothe total of the oxyalkylene group having 3-4 carbon atoms and theoxyethylene group is 50-100 wt %. The oxyalkylene group having 3-4carbon atoms and the oxyethylene group are randomly added. R denotes ahydrocarbon group having 1-4 atoms or a hydrogen atom, each different oridentical, and the ratio of the number of hydrogen atoms to the numberof the hydrocarbon groups is 0.15 or less.)

Furthermore, the present invention provides the aforementionedoil-in-water emulsified sunscreen cosmetic (H) further containingβ-alanyl-L-histidine and/or its salt in the amount of 0.1-4.5 wt % ofthe total amount of the cosmetic and the cosmetic's pH being less than8.

ADVANTAGEOUS EFFECTS

According to the present invention, it is possible to provide asunscreen cosmetic that improves the ultraviolet protection, stabilityof the base agent, and the sensation during use.

As a result, in the present invention, even whenphenylbenzimidazolesulfonic acid or its salt is added at the high levelof 5 wt %, the emulsification stability of the base agent improves, notto mention an increased ultraviolet protection due to the blend ratio.

Also, by selecting a specific surfactant and adding it at a specificcomposition ratio along with other essential ingredients, the hightemperature stability and usability of the prepared oil-in-wateremulsified composition are improved.

Furthermore, by adding a specific monoester oil, it is possible toprevent degradation of the appearance of the sunscreen cosmetic due tothe temperature cycling.

In addition, in the present invention, even when carnosine is added, itis possible to prevent an increase in the pH of the base agent due tocarnosine.

BEST MODE FOR CARRYING OUT THE INVENTION

The configuration of the present invention is described in detail below.

(A) Containing the following three types of surfactants (A-1)-(A-3) inthe amount of 1-6 wt % of the total amount of the cosmetic.

(A-1) A POE stearic ester having a POE mole number of 20-120

(A-2) Sorbitan tristearate

(A-3) Glyceryl stearate having a HLB of 5-8

Ingredients (A-1)-(A-3) are prior art ingredients of cosmetics and theyfunction as surfactants in the present invention.

Ingredient (A-3), i.e. glyceryl stearate having a HLB of 5-8, isprepared by mixing an arbitrary higher fatty acid with glyceryl stearateto adjust the HLB to 5-8.

These three types of surfactants are added in the amount of 1-6 wt % ofthe total amount of the cosmetic. If it is less than 1 wt %, then thehigh temperature stability becomes poor. On the other hand, if it isover 6 wt %, then a sticky sensation becomes noticeable during use. Thepreferable range is 1.5-5.5 wt %.

<Conditions of (1) of Claim 2>

Particularly, the ingredient (A-3) content is preferably 10-75 wt % ofthe total amount of ingredients (A-1), (A-2), and (A-3). Morepreferably, the ingredient (A-3) content is 20-70 wt % of the totalamount of ingredients (A-1), (A-2), and (A-3). If it is less than 10 wt%, then the high temperature stability becomes poor. On the other hand,if it is over 75 wt %, then not only the sensation during use(absorption and stickiness) deteriorates but the stability alsodeteriorates.

(B) Containing the following oil soluble ultraviolet absorbent, which issolid at room temperature, in the amount of 0.01-5 wt % of the totalamount of the cosmetic.

Bis-ethylhexyloxyphenolmethoxyphenyltriazine and/ortert-butylmethoxybenzoylmethane

In the present invention, there is no risk of the ultraviolet absorbentprecipitating as a solid at room temperature even if an oil solubleultraviolet absorbent that is solid at room temperature is added toimprove the ultraviolet protection.

The oil soluble ultraviolet absorbent used in the present invention isbis-ethylhexyloxyphenolmethoxyphenyltriazine and/ortert-butylmethoxybenzoylmethane, which are prior art ultravioletabsorbents.

The blend ratio of the aforementioned ultraviolet absorbent is 0.01-5 wt%, preferably 0.1-4.5 wt %, of the total amount of the cosmetic. If theblend ratio is 0.01 wt % or less, then effective ultraviolet protectioncannot be obtained, and if it is 5 wt % or more, then the stabilitydeteriorates (such as precipitation of crystals at low temperatures).

In the present invention, room temperature indicates 25° C.

(C) Containing the following oil soluble ultraviolet absorbent that isliquid at room temperature, in the amount of 1-14 wt % of the totalamount of the cosmetic.

Ethylhexyl methoxycinnamate and/or octocrylene

In the present invention, the aforementioned oil soluble ultravioletabsorbent that is liquid at room temperature is added to improve theultraviolet protection and solubility of said ingredient (B).

The oil soluble ultraviolet absorbent that is liquid at room temperatureused in the present invention is ethylhexyl methoxycinnamate and/oroctocrylene, which are prior art ultraviolet absorbents.

The blend ratio of the aforementioned ultraviolet absorbent is 1-14 wt%, preferably 3-12 wt %, of the total amount of the cosmetic. When theblend ratio is 1 wt % or less, then solubility of said ingredient (B)deteriorates and therefore the stability deteriorates (such asprecipitation of crystals at low temperatures). If the blend ratio isover 14 wt %, then the sensation during use (stickiness) due to thisingredient becomes prominent and the high temperature stability alsodeteriorates.

(D) Containing the following water soluble ultraviolet absorbent in theamount of 0.1-15 wt % of the total amount of the cosmetic.

Phenylbenzimidazolesulfonic acid or its salt

Furthermore, phenylbenzimidazolesulfonic acid or its salt, as a watersoluble ultraviolet absorbent, is added to the present invention. Thesalt is Na salt, Ka salt, and/or triethanolamine salt.

Phenylbenzimidazolesulfonic acid or its salt is added to further improvethe ultraviolet protection. At the same time, it turned out surprisinglythat the addition of this ultraviolet absorbent also contributed to animprovement in the stability of the base agent and usability.

The water soluble ultraviolet absorbent is phenylbenzimidazolesulfonicacid or its salt, which are prior art ultraviolet absorbents.

The blend ratio of the aforementioned ultraviolet absorbent is 0.1-5 wt%, preferably 0.5-3 wt %, of the total amount of the cosmetic. Thisaddition is to improve the ultraviolet protection. If the blend ratio isless than 0.1 wt %, then not only the ultraviolet protection cannot beobtained but also sufficient emulsification cannot be obtained andusability (absorption) also deteriorates. If the blend ratio is over 5wt %, then the sensation during use (stickiness) due to this ingredientbecomes prominent.

(E) Containing a higher alcohol having 14-24 carbon atoms.

In the present invention, it was discovered that the addition of ahigher alcohol having 14-24 carbon atoms, in addition to theaforementioned essential ingredients, improved the stability of the baseagent and usability.

This effect is not guaranteed if the number of carbon atoms is outsideof this range. A more preferable number of carbon atoms is 16-22.

Specific examples of preferable higher alcohols include cetanol, stearylalcohol, and behenyl alcohol.

<Condition (2) of Claim 2>

The blend ratio of the aforementioned higher alcohol {referred to asingredient (E)} is preferably 30-90 wt %, more preferably 35-85 wt %, ofthe total amount of ingredients (A-1), (A-2), and (A-3). If it is lessthan 30 wt %, then the high temperature stability cannot be secured. Onthe other hand, if it is over 90 wt %, then the stability overtemperature cycling deteriorates and poor absorption due to the higheralcohol affects the sensation during use.

<Claim 3>

(F) Containing the monoester oil represented by the following formula(1) in the amount of 0.2-9 wt % of the total amount of the cosmetic.

[Chemical formula 3]

R₁COOR₂  (1)

(In this formula, R₁ denotes an alkyl group having 5-11 carbon atoms,and R₂ denotes an alkyl group having 3-11 carbon atoms.)

It is preferable that the aforementioned monoester oil (referred to asingredient F) is further added to the present invention. The addition ofthis can prevent deterioration of the appearance due to temperaturecycling and also improve the sensation during use (absorption).Preferable ester oils are those whose R1 and R2 are alkyl groups having9 or less carbon atoms; and more preferable are 2-ethylhexyl2-ethylhexanoate and isononyl isononoate.

The blend ratio of the aforementioned monoester is 0.2-9 wt %,preferably 0.5-8 wt %, of the total amount of the cosmetic. If the blendratio is less than 0.2 wt %, then there is not enough effect onusability and stability. On the other hand, if the blend ratio is over 9wt %, then there is an adverse effect on the high temperature stability.

<Claim 4>

(G) Containing the random copolymer ether compound of ethylene glycoland propylene glycol represented by the following formula (2) in theamount of 0.2-9 wt % of the total amount of the cosmetic.

[Chemical formula 4]

RO-[(EO)_(m)(AO)_(n)]-OR  (2)

(In this formula, AO denotes an oxyalkylene group having 3-4 carbonatoms, EO denotes an oxyethylene group, m and n, respectively, areaverage addition mole numbers of said oxyalkylene group and oxyethylenegroup; also 1=<m=<70 and 1=<n=<70. The oxyalkylene group having 3-4carbon atoms and the oxyethylene group are randomly added. R denotes ahydrocarbon group having 1-4 atoms or a hydrogen atom, each different oridentical, and the ratio of the number of hydrogen atoms to the numberof the hydrocarbon groups is 0.15 or less.)

It is preferable that the aforementioned random copolymer ether compound(referred to as ingredient G) is further added to the present invention.By adding this, effects such as an improvement in the high temperaturestability, in the sensation during use (absorption and stickiness), andalso in the emulsification are achieved.

Preferable random copolymer ether compounds are those represented byformula (2) wherein m=14 and n=7, as well as m=17 and n=4.

The blend ratio of the aforementioned random copolymer ether compound is0.2-9 wt %, preferably 0.5-5 wt %, of the total amount of the cosmetic.If the blend ratio is less than 0.2 wt %, then there is not enougheffect on usability, stability, and emulsification. On the other hand,if the blend ratio is over 9 wt %, then there is an adverse effect onthe high temperature stability.

(H) Containing β-alanyl-L-histidine and/or its salt (trivial name:carnosine; referred to as ingredient H) in the amount of 0.1-4.5 wt % ofthe total amount of the cosmetic and the pH of the cosmetic is lowerthan 8.

The present invention is a sunscreen cosmetic. Condition (H) is acondition for the case where a prior art material carnosine is furtheradded, as an antioxidant and/or anti-wrinkling agent, to the sunscreencosmetic of the present invention.

That is, the present invention manifests a prominent effect ofpreventing an increase in the pH of the base agent even when carnosine,which is an basic dipeptide, is added. That is, the increase in the pHof the cosmetic of the sunscreen cosmetic of the present invention canbe controlled under 8 even when carnosine is added and therefore this isincorporated as condition (H).

The aforementioned effect is manifested when carnosine, ingredient (H),is added in the amount of 0.1-4.5 wt % of the total amount of thecosmetic. In particular, the pH increase due to this ingredient can bekept under 8 even when the blend ratio is as high as 1-3 wt %, whichmakes the present invention very significant.

The oil-in-water emulsified sunscreen cosmetic of the present inventionis prepared as an oil-in-water emulsified composition by adding waterand water soluble cosmetic ingredients, oil ingredients, and powder tothe aforementioned essential ingredients, followed by mixing by aconventional method.

The blend ratio of water is 20-80 wt %, preferably 30-60 wt %, of thetotal amount of the cosmetic.

In addition to the aforementioned essential ingredients, otheringredients used in cosmetics can be blended as necessary in theoil-in-water sunscreen cosmetic of the present invention; examples ofsuch ingredients include powder ingredients, liquid fats and oils, solidfats and oils, waxes, hydrocarbons, higher fatty acids, higher alcohols,esters, silicones, anionic surfactants, cationic surfactants, ampholyticsurfactants, nonionic surfactants, humectants, water-soluble polymers,thickeners, coating agents, ultraviolet absorbents, sequestering agents,lower alcohols, polyhydric alcohols, sugars, amino acids, organicamines, polymer emulsions, pH adjusting agents, skin nutrients,vitamins, antioxidants, antioxidation assistants, perfumes, and water;and the endermic liniment can be prepared for the target formulationwith a conventional method. Specific ingredients which can be blended inare listed below. The skin cosmetic of the present invention can beprepared by blending the aforementioned essential ingredients and anyone, two or more of the following ingredients.

Examples of the powder ingredients include inorganic powders (forexample, talc, kaolin, mica, sericite, muscovite, phlogopite, syntheticmica, lepidolite, biotite, vermiculite, magnesium carbonate, calciumcarbonate, aluminum silicate, barium silicate, calcium silicate,magnesium silicate, strontium silicate, tungstic acid metal salt,magnesium, silica, zeolite, barium sulfate, firing calcium sulfate(calcined gypsum), calcium phosphate, fluorine-apatite, hydroxy apatite,ceramic powder, metallic soaps (for example, myristic acid zinc, calciumpalmitate, and aluminum stearate), and boron nitride); organic powders(for example, polyamide resin powder (nylon powder), polyethylenepowder, poly-methyl methacrylate powder, polystyrene powder, powders ofthe copolymer resin of styrene and acrylic acid, benzoguanamine resinpowder, polytetrafluoroethylene powder, and cellulose powder); inorganicwhite pigments (for example, titanium dioxide and zinc oxide); inorganicred pigments (for example, iron oxide (red iron oxide) and irontitanate); inorganic brown pigments (for example, γ-iron oxide);inorganic yellow pigments (for example, yellow iron oxide and loess);inorganic black pigments (for example, black iron oxide and low oxidesof titanium); inorganic purple pigments (for example, manganese violet,cobalt violet); inorganic green pigments (for example, chromium oxide,chromium hydroxide, and cobalt titanate); inorganic blue pigments (forexample, ultramarine blue and Berlin blue); pearl pigment (for example,titania coated mica, titania coated bismuth oxychloride, titania coatedtalc, coloration titania coated mica, bismuth oxychloride, fish scaleflakes); metal powder pigments (for example, aluminium powder, copperpowder); organic pigments such as Zr, barium or aluminium rake (forexample, organic pigments such as red 201, red 202, red 204, red 205,red 220, red 226, red 228, red 405, orange 203, orange 204, yellow 205,yellow 401 and blue 404, as well as red 3, red 104, red 106, red 227,red 230, red 401, red 505, orange 205, yellow 4, yellow 5, yellow 202,yellow 203, green 3 and blue 1; and natural colors (for example,chlorophyll and β-carotene).

Examples of the liquid fats and oils include avocado oil, tsubaki oil,turtle fatty acid, macademia nut oil, corn oil, mink oil, olive oil,rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil,sasanqua oil, castor oil, linseed oil, safflower oil, cotton seed oil,perilla oil, soybean oil, peanut oil, tea seed oil, Japanese nutmeg oil,rice bran oil, Chinese gimlet oil, Japanese gimlet oil, jojoba oil, germoil, and triglycerin.

Examples of the solid fats and oils include cacao butter, coconut oil,hydrogenated coconut oil, palm oil, palm kernel oil, Japanese core waxnucleus oil, hydrogenated oil, Japanese core wax, and hydrogenatedcastor oil.

Examples of the waxes include beeswax, candelilla wax, cotton wax,carnauba wax, bayberry wax, tree wax, whale wax, montan wax, bran wax,lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax,lanolin fatty acid isopropyl ester, hexyl laurate, reduced lanolin,jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol ether, POElanolin alcohol acetate, POE cholesterol ether, lanolin fatty acidpolyethylene glycol, and POE hydrogenated lanolin ethyl alcohol ether.

Examples of the hydrocarbon oils include liquid petrolatum, ozocerite,squalane, pristane, paraffin, ceresin, squalene, petrolatum, andmicrocrystallin wax.

Examples of the higher fatty acids include lauric acid, myristic acid,palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid,tall oil fatty acid, isostearic acid, linolic acid, linoleic acid,eicosapentaenoic acid (EPA), and docosahexaenoic acid (DHA).

Examples of the higher alcohols include straight chain alcohols (forexample, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenylalcohol, myristyl alcohol, oleyl alcohol, and cetostearyl alcohol) andbranched chain ethyl alcohols (for example, mono stearyl glycerin ether(batyl alcohol), 2-decyltetradecynol, lanolin alcohol, cholesterol,phytosterol, hexyl dodecanol, iso stearyl alcohol, and octyl dodecanol).

Examples of the ester oils include isopropyl myristate, cetyl octanoate,octyl dodecyl myristate, isopropyl palmitate, butyl stearate, hexyllaurate, myristil myristate, decyl oleate, dimethyl hexyl decyloctanoate, cetyl lactate, myristil lactate, lanolin acetate, iso cetylstearate, iso cetyl isostearate, cholesteryl 12-hydroxystearate,di-2-ethylene glycol ethylhexanoate, dipentaerythritol fatty acid ester,n-alkylene glycol monoisostearate, neopentyl glycol dicaprate,diisostearyl malate, glyceryl di-2-heptylundecanoate, trimethylolpropanetri-2-ethyl hexanoate, trimethylolpropane triisostearate,tetra-2-pentaerythritol ethylhexanoate, glycerin tri2-ethylhexanoate,glyceryl trioctanoate, glycerin triisopalmitate, trimethylolpropanetriisostearate, cetyl 2-ethyl hexanoate, 2-ethylhexyl palmitate,glycerin trimyristate, tri-2-heptyl undecanoic acid glyceride, methylcastor oil fatty acid, oleyl oleate, aceto glyceride, 2-heptylundecylpalmitate, diisobutyl adipate, 2-octyldodecyl N-lauroyl-L-glutamate,di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate,2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate,diisopropyl sebacate, 2-ethylhexyl succinate, and triethyl citrate.

Examples of the silicone oils include chain polysiloxanes (for example,dimethylpolysiloxane, methylphenyl polysiloxane, and diphenylpolysiloxane); ring polysiloxanes (for example,octamethylcyclotetrasiloxane, decamethyl cyclopenta siloxane, anddodecamethyl cyclohexa siloxane), silicone resins forming athree-dimensional network structure, silicone rubbers, and variousmodified polysiloxanes (amino-modified polysiloxane, polyether-modifiedpolysiloxane, alkyl-modified polysiloxane, and fluorine-modifiedpolysiloxane).

Examples of the anionic surfactants include fatty acid soaps (forexample, sodium laurate and sodium palmitate); higher alkyl sulfuricester salts (for example, sodium lauryl sulfate and potassiumlaurylsulfate); alkylether sulfuric ester salts (for example,POE-triethanolamine laurylsulfate and sodium POE-lauryl sulfate); N-acylsarcosinic acids (for example, sodium N-lauroyl sarcosinate); higherfatty acid amide sulfonic acid salts (for example, sodium N-myristoylN-methyl taurate, sodium cocoyl methyl taurate, and sodium laurylmethyltaurate); phosphoric ester salts (for example, sodium POE-oleyl etherphosphate and POE stearyl ether phosphoric acid); sulfosuccinates (forexample sodium di-2-ethylhexylsulfosuccinate, sodium monolauroylmonoethanol amide polyoxyethylene sulfosuccinate, and sodium laurylpolypropylene glycol sulfosuccinate); alkyl benzene sulfonates (forexample, sodium linear dodecyl benzene sulfonate, triethanolamine lineardodecyl benzene sulfonate, linear dodecyl benzene sulfonic acid); higherfatty acid ester sulfates (for example, hydrogenated coconut oilaliphatic acid glycerin sodium sulfate); N-acyl glutamates (for example,mono sodium N-lauroylglutamate, disodium N-stearoylglutamate, and sodiumN-myristoyl-L-glutamate); sulfated oils (for example, turkey red oil);POE-alkylether carboxylic acid; POE-alkylarylether carboxylate; α-olefinsulfonate; higher fatty acid ester sulfonates; sec-alcohol sulfates;higher fatty acid alkyl amide sulfates; sodium lauroyl monoethanolaminesuccinates; ditriethanolamine N-palmitoylaspartate; and sodiumcaseinate.

Examples of the cationic surfactants include alkyltrimethylammoniumsalts (for example, stearyltrimethyl ammonium chloride andlauryltrimethyl ammonium chloride) alkylpyridinium salts (for example,cetylpyridinium chloride), distearyldimethylammonium chloridedialkyldimethylammonium salt; poly(N,N′-dimethyl3-methylenepiperidinium)chloride; alkyl quaternary ammonium salts; alkyldimethylbenzyl ammonium salts; alkyl isoquinolinium salts;dialkylmorpholine salts; POE alkyl amines; alkyl amine salts; polyaminefatty acid derivatives; amylalcohol fatty acid derivatives; benzalkoniumchloride; and benzethonium chloride.

Examples of the ampholytic surfactants include: imidazoline typeampholytic surfactants (for example, 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium salt and 2-cocoyl-2-imidazoliniumhydroxidel-carboxyethyloxy 2 sodium salt); and betaine type surtactants(for example, 2-heptadecyl-n-carboxymethyl-n-hydroxyethyl imidazoliniumbetaine, lauryldimethylaminoacetic acid betaine, alkyl betaine, amidebetaine, and sulfobetaine).

Examples of the hydrophilic nonionic surface active agents include:polyglycerin fatty acid esters such as hexaglyceryl monolaurate (HLB14.5), hexaglyceryl monomyristate (HLB 11), hexyglyceryl monostearate(HLB 9.0), hexaglyceryl monooleate (HLB 9.0), decaglyceryl monolaurate(HLB 15.5), decaglyceryl monomyristate (HLB 14.0), decaglycerylmonostearate (HLB 12.0), decaglyceryl monoisostearate (HLB 12.0),decaglyceryl monooleate (HLB 12.0), decaglyceryl distearate (HLB 9.5),and decaglyceryl diisostearate (HLB 10.0);

polyoxyethylene glycerin fatty acid esters such as polyoxyethylene(hereafter abbreviated as POE) glyceryl monostearate (5) (HLB 9.5), POE(15) glyceryl monostearate (HLB 13.5), POE (5) glyceryl monooleate (HLB9.5), and POE (15) glyceryl monooleate (HLB 14.5);

polyoxyethylene sorbitan fatty acid esters such as POE (20) sorbitanmonococoate (HLB 16.9), POE (20) sorbitan monopalmitate (HLB 15.6), POE(20) sorbitan monostearate (HLB 14.9), POE (6) sorbitan monostearate(HLB 9.5), POE (20) sorbitan tristearate (HLB 10.5), POE (20) sorbitanmonoisostearate (HLB 15.0), POE (20) sorbitan monooleate (HLB 15.0), POE(6) sorbitan monooleate (HLB 10.0), and POE (20) sorbitan trioleate (HLB11.0);

polyoxyethylene sorbit fatty acid esters such as POE (6) sorbitmonolaurate (HLB 15.5), POE (60) sorbit tetrastearate (HLB 13.0), POE(30) sorbit tetraoleate (HLB 11.5), POE (40) sorbit tetraoleate (HLB12.5), and POE (60) sorbit tetraoleate (HLB 14.0);

polyoxyethylene lanolin/lanolin alcohol/beeswax derivatives such as POE(10) lanolin (HLB 12.0), POE (20) lanolin (HLB 13.0), POE (30) lanolin(HLB 15.0), POE (5) lanolin alcohol (HLB 12.5), POE (10) lanolin alcohol(HLB 15.5), POE (20) lanolin alcohol (HLB 16.0), POE (40) lanolinalcohol (HLB 17.0), and POE (20) sorbit beeswax (HLB 9.5);

polyoxyethylene castor oils/hydrogenated oils such as POE (20) castoroil (HLB 10.5), POE (40) castor oil (HLB 12.5), POE (50) castor oil (HLB14.0), POE (60) castor oil (HLB 14.0), POE (20) hydrogenated castor oil(HLB 10.5), POE (30) hydrogenated castor oil (HLB 11.0), POE (40)hydrogenated castor oil (HLB 13.5), POE (60) hydrogenated castor oil(HLB 14.0), POE (80) hydrogenated castor oil (HLB 16.5), and POE (40)hydrogenated castor oil (100) hydrogenated castor oil (HLB 16.5);

polyoxyethylene sterols/hydrogenated sterols such as POE (5) phytosterol(HLB 9.5), POE (10) phytosterol (HLB 12.5), POE (20) phytosterol (HLB15.5), POE (30) phytosterol (HLB 18.0), POE (25) phytostanol (HLB 14.5),and POE (30) cholestanol (HLB 17.0);

polyoxyethylene alkyl ethers such as POE (2) lauryl ether (HLB 9.5), POE(4.2) lauryl ether (HLB 11.5), POE (9) lauryl ether (HLB 14.5), POE(5.5) cetyl ether (HLB 10.5), POE (7) cetyl ether (HLB 11.5), POE (10)cetyl ether (HLB 13.5), POE (15) cetyl ether (HLB 15.5), POE (20) cetylether (HLB 17.0), POE (23) cetyl ether (HLB 18.0), POE (4) stearyl ether(HLB 9.0), POE (20) stearyl ether (HLB 18.0), POE (7) oleyl ether (HLB10.5), POE (10) oleyl ether (HLB 14.5), POE (15) oleyl ether (HLB 16.0),POE (20) oleyl ether (HLB 17.0), POE (50) oleyl ether (HLB 18.0), POE(10) behenyl ether (HLB 10.0), POE (20) behenyl ether (HLB 16.5), POE(30) behenyl ether (HLB 18.0), POE (2) (c12-15) alkyl ether (HLB 9.0),POE (4) (c12-15) alkyl ether (HLB 10.5), POE (10) (c12-15) alkyl ether(HLB15.5), POE (5) secondary alkyl ether (HLB 10.5), POE (7) secondaryalkyl ether (HLB 12.0), POE (9) alkyl ether (HLB 13.5), and POE (12)alkyl ether (HLB 14.5);

polyoxyethylene polyoxypropylene alkyl ethers such as polyoxyethylene(hereafter abbreviated as POE) (1) polyoxypropylene (hereafterabbreviated as POP) (4) cetyl ether (HLB 9.5), POE (10) POP (4) cetylether (HLB 10.5), POE (20) POP (8) cetyl ether (HLB 12.5), POE (20) POP(6) decyltetradecyl ether (HLB 11.0), and POE (30) POP (6)decyltetradecyl ether (HLB 12.0);

polyethylene glycol fatty acid esters such as polyethylene glycol(hereafter abbreviated as PEG) (10) (HLB 12.5), PEG (10) monostearate(HLB 11.0), PEG (25) monostearate (HLB 15.0), PEG (40) monostearate (HLB17.5), PEG (45) monostearate (HLB 18.0), PEG (55) monostearate (HLB18.0), PEG (10) monooleate (HLB 11.0), PEG distearate (HLB 16.5), andPEG diisostearate (HLB 9.5);

and polyoxyethylene glyceryl isostearates such as PEG (8) glycerylisostearate (HLB 10.0), PEG (10) glyceryl isostearate (HLB 10.0), PEG(15) glyceryl isostearate (HLB 12.0), PEG (20) glyceryl isostearate (HLB13.0), PEG (25) glyceryl isostearate (HLB 14.0), PEG (30) glycerylisostearate (HLB 15.0), PEG (40) glyceryl isostearate (HLB 15.0), PEG(50) glyceryl isostearate (HLB 16.0), and PEG (60) glyceryl isostearate(HLB 16.0).

Examples of the lipophilic surfactant include POE (2) stearyl ether (HLB4.0), self emulsified propylene glycol monostearate (HLB 4.0), glycerylmyristate (HLB 3.5), glyceryl monostearate (HLB 4.0), self emulsifiedglyceryl monostearate (HLB 4.0), glyceryl monoisostearate (HLB 4.0),glyceryl monooleate (HLB 2.5), hexaglyceryl tristearate (HLB 2.5),decaglyceryl pentastearate (HLB 3.5), decaglyceryl pontaisostearate (HLB3.5), decaglyceryl pentaoleate (HLB 3.5), sorbitan monostearate (HLB4.7), sorbitan tristearate (HLB 2.1), sorbitan monoisostearate (HLB5.0), sorbitan sesquiisostearate (HLB 4.5), sorbitan monooleate (HLB4.3), POE (6) sorbit hexastearate (HLB 3.0), POE (3) castor oil (HLB3.0), PEG (2) monostearate (HLB 4.0), ethylene glycol monostearate (HLB3.5), and PEG (2) stearate (HLB 4.5).

Examples of the humectant include polyethylene glycol, propylene glycol,glycerin, 1,3-butylene glycol, xylitol, sorbitol, maltitol, chondroitinsulfate, hyaluronic acid, mucoitin sulfuric acid, charonic acid,atelocollagen, cholesteryl-12-hydroxy stearate, sodium lactate, bilesalt, dl-pyrrolidone carboxylic acid salt, short chain soluble collagen,diglycerin (EO)PO adduct, chestnut rose fruit extract, yarrow extract,and sweet clover extract.

Examples of the natural water-soluble polymer include: plant-typepolymers (for example, gum arabic, gum tragacanth, galactan, guar gum,carob gum, karaya gum, carrageenan, pectin, agar, quince seed (Cycloniaoblonga), algae colloids (brown algae extract), starches (rice, corn,potato, and wheat), and glycyrrhizic acid); microorganism-type polymers(for example, xanthan gum, dextran, succinoglucan, and pullulan); andanimal-type polymers (for example, collagen, casein, albumin, andgelatin).

Examples of the semisynthetic water-soluble polymers include:starch-type polymers (for example, carboxymethyl starch andmethylhydroxypropyl starch); cellulosic polymers (for example, methylcellulose, ethyl cellulose, methylhydroxypropyl cellulose, hydroxyethylcellulose, cellulose sodium sulfate, hydroxypropyl cellulose,carboxymethyl-cellulose, sodium carboxymethyl cellulose, crystalcellulose, and cellulose powder); and alginic acid-type polymers (forexample, sodium alginate and propyleneglycol alginate).

Examples of the synthetic water-soluble polymers include: vinyl polymers(for example, polyvinyl alcohol, polyvinyl methyl ether,polyvinylpyrrolidone, carboxy vinyl polymer); polyoxyethylene-typepolymers (for example, a copolymer of polyethylene glycol 20,000,40,000, or 60,000 and polyoxyethylene polyoxypropylene); acrylicpolymers (for example, sodium polyacrylate, polyethylacrylate, andpolyacrylamide); polyethyleneimine; and cationic polymers.

Examples of the thickeners include: gum arabic, carrageenan, karaya gum,gum tragacanth, carob gum, quince seed (Cyclonia oblonga), casein,dextrin, gelatin, sodium pectate, sodium arginate, methyl cellulose,ethyl cellulose, CMC, hydroxy ethyl cellulose, hydroxypropyl cellulose,PVA, PVM, PVP, sodium polyacrylate, carboxy vinyl polymer, locust beangum, guar gum, tamarind gum, cellulose dialkyl dimethylammonium sulfate,xanthan gum, aluminum magnesium silicate, bentonite, hectorite, AlMgsilicate (beagum), laponite, and silicic acid anhydride.

Examples of the ultraviolet absorbents include the following compounds.

(1) Benzoic Acid-Type Ultraviolet Absorbents

Examples include paraminobenzoic acid (hereafter abbreviated as PABA),PABA monoglycerin ester, N,N-dipropoxy PABA ethyl ester, N,N-diethoxyPABA ethyl ester, N,N-dimethyl PABA ethyl ester, N,N-dimethyl PABA butylester, and N,N-dimethyl PABA ethyl ester.

(2) Anthranilic Acid-Type Ultraviolet Absorbents

Examples include homo mentyl-N-acetyl anthranilate.

(3) Salicylic Acid-Type Ultraviolet Absorbents

Examples include amyl salicylate, mentyl salicylate, homo mentylsalicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, andp-isopropanol phenyl salicylate.

(4) Cinnamic Acid-Type Ultraviolet Absorbents

Examples include octyl cinnamate, ethyl-4-isopropyl cinnamate,methyl-2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate,methyl-2,4-diisopropyl cinnamate, propyl-p-methoxy cinnamate,isopropyl-p-methoxy cinnamate, isoamyl-p-methoxy cinnamate,octyl-p-methoxy cinnamate, 2-ethylhexyl-p-methoxy cinnamate,2-ethoxyethyl-p-methoxy cinnamate, cyclohexyl-p-methoxy cinnamate,ethyl-α-cyano-β-phenyl cinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, and glyceryl mono-2-ethyl hexanoyl-diparamethoxy cinnamate.

(5) Triazine-Type Ultraviolet Absorbents

For example, bisresorsinyl triazine.More specifically,bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)1,3,5-triazine,2, 4,6-tris {4-(2-ethylhexyloxycarbonyl)anilino}1,3,5-triazine, etc.

(6) Other Ultraviolet Absorbents

Examples include 3-(4′-methylbenzylidene)-d, 1-camphor, 3-benzylidene-d,1-camphor, 2-phenyl-5-methyl benzoxazole, 2,2′-hydroxy-5-methylphenylbenzotriazol, 2-(2′-hydroxy-5′-t-octylphenyl) benzotriazol,2-(2′-hydroxy-5′-methylphenyl benzotriazol, dibenzaladine,dianisoylmethane, 4-methoxy-4′-t-butyl dibenzoyl-methane, and5-(3,3-dimethyl-2-norbornylidene)-3-pentane-2-one. Also, pyridazinederivatives such as dimorpholinopyridazinone.

Examples of the sequestering agents include 1-hydroxyethanel-diphosphonic acid, 1-hydroxy ethanel-diphosphonic acidtetrasodium salt, disodium edetate, trisodium edetate, tetrasodiumedetate, sodium citrate, sodium polyphosphate, sodium metaphosphate,gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinicacid, and trisodium ethylenediaminehydroxyethyl triacetate.

Examples of the lower alcohols include ethanol, propanol, isopropanol,isobutyl alcohol, and t-butyl alcohol.

Examples of the polyhydric alcohols include: dihydric alcohols (forexample, ethylene glycol, propylene glycol, trimethylene glycol,1,2-butylene glycol, 1,3-butylene glycol, tetramethylene glycol,2,3-butylene glycol, pentamethylene glycol, 2-butene-1,4-diol, hexyleneglycol, and octylene glycol); trihydric alcohols (for example, glycerinand trimethylolpropane); tetrahydric alcohols (for example,pentaerythritol such as 1,2,6-hexanetriol); pentahydric alcohols (forexample, xylitol); hexahydric alcohols (for example, sorbitol,mannitol); polyhydric alcohol polymers (for example, diethylene glycol,dipropylene glycol, triethylene glycol, polypropylene glycol,tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin,tetraglycerin, and polyglycerin); dihydric alcohol alkylethers (forexample, ethylene glycol monomethyl ether, ethylene glycol monoethylether, ethylene glycol monobutyl ether, ethylene glycol monophenylether, ethylene glycol monohexyl ether, ethylene glycol mono 2-methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzylether, ethylene glycol isopropyl ether, ethylene glycol dimethylether,ethylene glycol diethyl ether, and ethylene glycol dibutyl ether);dihydric alcohol alkylethers (for example, diethylene glycol monomethylether, diethylene glycol monoethyl ether, diethylene glycol monobutylether, diethylene glycol dimethyl ether, diethylene glycol diethylether, diethylene glycol butyl ether, diethylene glycol methylethylether, triethylene glycol monomethyl ether, triethylene glycol monoethylether, propylene glycol monomethyl ether, propylene glycol monoethylether, propylene glycol monobutyl ether, propylene glycol isopropylether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether,dipropylene glycol butyl ether); dihydric alcohol ether esters (forexample, ethylene glycol monomethyl ether acetate, ethylene glycolmonoethyl ether acetate, ethylene glycol monobutyl ether acetate,ethylene glycol monophenyl ether acetate, ethylene glycol diadipate,ethylene glycol disuccinate, diethylene glycol monoethyl ether acetate,diethylene glycol monobutyl ether acetate, propylene glycolmonomethylether acetate, propylene glycol monoethyl ether acetate, propyleneglycol monopropyl ether acetate, and propylene glycol monophenyl etheracetate); glycerin mono alkyl ethers (for example, chimyl alcohol,selachyl alcohol, and batyl alcohol); sugar alcohols (for example,sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose,fructose, starch amylolysis sugar, maltose, xylitose, and alcoholprepared by the reduction of starch amylolysis sugar); glysolid;tetrahydro furfuryl alcohol; POE-tetrahydro furfuryl alcohol; POP-butylether; POP/POE-butyl ether; tripolyoxypropylene glycerin ether;POP-glycerin ether, POP-glycerin ether phosphoric acid; POP/POE-pentaneerythritol ether, and polyglycerin.

Examples of the monosaccharides include: trioses (for example,D-glyceryl aldehyde and dihydroxyacetone); tetroses (for example,D-etythrose, D-erythrulose, D-threose, and erythritol); pentoses (forexample, L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose,D-ribulose, D-xylulose, and L-xylulose); hexoses (for example,D-glucose, D-talose, D-psicose, D-galactose, D-fructose, L-galactose,L-mannose, and D-tagatose); heptoses (for example, aldoheptose andheprose); octoses (for example, octurose); deoxysugars (for example,2-deoxy-D-ribose, 6-deoxy-L-galactose, and 6-deoxy-L-mannose); aminosugars (for example, D-glucosamine, D-galactosamine, sialic acid, aminouronic acid, and muramic acid); and uronic acid (for example,D-glucuronic acid, D-mannuronic acid, L-guluronic acid, D-galacturonicacid, and L-iduronic acid).

Examples of the oligosaccharides include sucrose, umbelliferose,lactose, planteose, isolignoses, α,α-trehalose, raffinose, lignoses,umbilicine, stachyose and verbascose.

Examples of the polysaccharides include cellulose, quince seed,chondroitin sulfate, starch, galactan, dermatan sulfate, glycogen, gumarabic, heparan sulfate, hyaluronic acid, traganth gum, keratan sulfate,chondroitin, xanthan gum, mucoitin sulfuric acid, guar gum, dextran,kerato sulfate, locustbean gum, succinoglucane, and charonic acid.

Examples of amino acids include neutral amino acids (for example,threonine and cysteine) and basic amino acids (for example,hydroxylysine). Examples of the amino acid derivatives include sodiumacyl sarcosinate (sodium N-lauroyl sarcosinate), acyl glutamate, sodiumacyl β-alanine, glutathione, and pyrrolidone carboxylic acid.

Examples of the organic amines include monoethanolamine, diethanolamine,triethanolamine, morpholine, triisopropanolamine,2-amino-2-methyl-1,3-propanediol, and 2-amino-2-methyl-1-propanol.

Examples of polymer emulsions include acrylic resin emulsions, ethylpolyacrylate emulsions, acryl resin liquids, polyacrylic alkyl esteremulsions, polyvinyl acetate resin emulsions, and natural rubber latex.

Examples of the pH adjustment agents include buffers such as lacticacid-sodium lactate, citric acid-sodium citrate, and succinicacid-sodium succinate.

Examples of vitamins include vitamin A, B1, B2, B6, C and E as well astheir derivatives, pantothenic acid and its derivatives, and biotin.

Examples of the antioxidants include tocopherols, dibutylhydroxytoluene, butyl hydroxyanisole, and gallic ester.

Examples of antioxidation assistants include phosphoric acid, citricacid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaricacid, cephalin, hexametaphosphate, phytic acid, and ethylene diaminetetraacetic acid.

Examples of other possible ingredients include antiseptics(methylparaben, ethylparaben, butylparaben, and phenoxyethanol);anti-inflammatory agents (for example, glycyrrhizic acid derivatives,glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol,zinc oxide, and allantoin); whitening agents (for example, creepingsaxifrage extract and arbutin); various extracts (for example,Phellodendri Cortex, goldthread, lithospermum root, Paeonia lactiflora,Swertia japonica, Birch, sage, loquat, carrot, aloe, Malva sylvestris,Iris, grape, Coix ma-yuen, sponge gourd, lily, saffron, Cnidiumofficinale, sheng jiang, Hypericum erectum, Ononis, garlic, Guineapepper, chen pi, Ligusticum acutilobum, and seaweed), activators (royaljelly, photosensitive substances, and cholesterol derivatives); bloodcirculation promoting agents (for example, nonyl acid valenyl amide,nicotinic acid benzyl esters, nicotinic acid β-butoxy ethyl esters,capsaicin, gingeron, cantharis tincture, Ichthammol, tannic acid,α-borneol, tocopherol nicotinate, inositol hexanicotinate, cyclandelate,cinnarizine, tolazoline, acetylcholine, verapamil, cepharanthine, andγ-orizanol); anti-seborrhea agents (for example, sulfur and thiantol);and antiinflammatory agents (for example, tranexamic acid, thiotaurine,and hypotaurine).

The product form of the sunscreen cosmetic of the present invention isnot limited. Examples include creams, emulsions, and lotions, and creamsare preferable in terms of stability and the sensation during use.

Examples Preparation Method

Using the formulations shown in the tables, the 0 part, heated up to 85°C. and melted, was mixed into the W part, which had been heated up to75° C. and dissolved, and emulsified; the P part was mixed into this andquickly cooled down to 30° C. (refer to the table for the relationshipbetween the ingredients and the parts) to prepare an oil-in-wateremulsified sunscreen cosmetic. The following evaluation tests wereconducted.

In the part column of the tables, W denotes water phase ingredients, Odenotes oil phase ingredients, and P denotes powder ingredients.

1. High Temperature Stability

The cosmetics were put into glass tubes and stored in thermostatic bathsset to 50° C., 40° C., and 25° C. for one month; after one month theywere checked for separation. Stability was evaluated based on thefollowing criteria.

⊚: No separation is observed under any storage conditions.

◯: Those stored at 50° C. are separated, but separation is not observedwith other temperature conditions.

Δ: Those stored at 50° C. and 40° C. are separated, but no separation isobserved with those stored at 25° C.

X: Separation is observed under all the conditions.

2. Stability Under Temperature Cycling

The cosmetics were put into glass tubes and stored under temperaturecycling (5° C.-45° C., 2 cycles/day, holding at 5° C. and 45° C. for twohours); after two weeks, one month, and two months, they were comparedwith those stored at 25° C. To compare the states of the samples, theywere applied thinly on a black board and smoothness was evaluated.

⊚: No difference even with those stored for two months.

◯: No difference up to one month, but those stored for two monthsexhibit unevenness.

Δ: No difference up to two weeks, but those stored for one month exhibitunevenness.

X: Those stored for two weeks exhibit unevenness.

3. Emulsified Particle Size

The emulsified particle size of the cosmetics immediately afterpreparation was evaluated by means of microscopic observation.

⊚: 1 micrometer or less

◯: Mostly 1 micrometer or less, although some emulsified particleshaving a size of 2-3 micrometers are observed

Δ: Mostly 3 micrometers or less, with many particles having a size of 1micrometer or more

X: Many emulsified particles having a size of 3 micrometers or more areobserved.

4. pH

The pH of the cosmetics immediately after the preparation was measuredby using a HORIBA pH Meter F-13 (from HORIBA, Ltd.).

5. Sensation During Use (Absorption)

A panel of 10 specialists applied the cosmetics on their faces andjudged the sensation of good absorption during use based on thefollowing criteria.

⊚: 9 or more panelists reported good absorption.

◯: 6 or more and less than 9 panelists reported good absorption.

Δ: 4 or more and less than 6 panelists reported good absorption.

X: Less than 4 panelists reported good absorption.

6. Sensation During Use (Stickiness)

A panel of 10 specialists applied the cosmetics on their faces andjudged the non-sticky sensation after application based on the followingcriteria.

⊚: 9 or more panelists reported non-stickiness.

◯: 6 or more and less than 9 panelists reported non-stickiness.

Δ: 4 or more and less than 6 panelists reported non-stickiness.

X: Less than 4 panelists reported non-stickiness.

7. Low Temperature Stability

The cosmetics were put into glass tubes and stored for three months at−20° C.; after one month a polarizing microscope was used to checkwhether or not crystals had precipitated; the evaluation was conductedbased on the following criteria.

◯: No crystalline precipitation is observed.

X: Crystalline precipitation is observed.

The following tables show the formulations of the cosmetics and theaforementioned evaluation results. In the formulations, prior artcosmetic raw materials and the following commercial products were used.

PEG40 stearate: NIKKOL MYS-40V (Nikko Chemicals Co., Ltd.)PEG100 stearate: NIKKOL MYS-100V (Nikko Chemicals Co., Ltd.)Sorbitan tristearate: NIKKOL SS-30V (Nikko Chemicals Co., Ltd.)Self emulsified glyceryl stearate: Tegin TV (Nikko Chemicals Co., Ltd.)

Tert-butylmethoxybenzoylmethane: Parsol 1789 (DSM Nutrition Japan Co.,Ltd.)

Bis ethylhexyloxyphenol methoxyphenyl Triazine: Tinosorb S (CibaSpecialty Chemicals Co., Ltd.)

Octocrylene: Parsol 340 (DSM Nutrition Japan Co., Ltd.)

Ethylhexyl methoxycinnamate: Parsol MCX (DSM Nutrition Japan Co., Ltd.)Phenylbenzimidazolesulfonic acid: Eusolex 232 (Merck)2-ethylhexyl 2-ethylhexanoate: KAK88SX (Kokyu Alcohol Kogyo Co., Ltd.)Isononyl isononanoate: KAK99SX (Kokyu Alcohol Kogyo Co., Ltd.)

Carnosine: Dragosine 2/060700 (Symrise)

Myristyl myristate: Crodamol. MM-P (Croda Japan KK) Dimeticone:KF-96A-6T (Shin-Etsu Chemical Co., Ltd.)Titanium oxide: Titanium Oxide MT-062 (Tayca Corporation)

Example 1 and Comparative examples 1-1, 1-2, and 1-3

TABLE 1-1 Condition (A) in claim 1 Comparative Comparative ComparativePart Ingredient Example 1 example 1-1 example 1-2 example 1-3 O A-1PEG40 stearate 1.1 2.5 — 1.6 O PEG100 stearate — — — — O A-2 Sorbitantristearate 1 1.1 1 — O A-3 Self emulsified glyceryl stearate 2.5 — 3.63 O B Tert-butylmethoxybenzoylmethane 2 2 2 2 O Bis ethylhexyloxyphenolmethoxyphenyl triazine 0.5 0.5 0.5 0.5 O C Octocrylene 5 5 5 5 OEthylhexyl methoxycinnamate — — — — W D Phenylbenzimidazolesulfonic acid2 2 2 2 O E Stearyl alcohol 0.5 0.5 0.5 0.5 O Behenyl alcohol 2 2 2 2 OCetanol — — — — O F 2-ethyhexyl 2-ethylhexanoate — — — — O Isononylisononanoate — — — — W G PEG/PPG-14/7 dimethyl ether — — — — WPEG/PPG-17/4 dimethyl ether — — — — W H Carnosine — — — — W OtherGlycerin 7 7 7 7 W Dipropylene glycol 5 5 5 5 W Butylene glycol 8 8 8 8W Xanthan gum 0.15 0.15 0.15 0.15 O Myristyl myristate 2 2 2 2 OMicrocrystalline wax 1 1 1 1 O Dimeticone 3 3 3 3 O Squalane 5 5 5 5 WTriethanolamine 1.2 1.2 1.2 1.2 P Titanium oxide 1 1 1 1 P Sphericalcellulose 0.5 0.5 0.5 0.5 W Edetate 0.1 0.1 0.1 0.1 W Phenoxy ethanol0.5 0.5 0.5 0.5 W Sodium pyrosulfite 0.003 0.003 0.003 0.003 WHexametaphosphoric soda 0.1 0.1 0.1 0.1 P Iron oxide (red) 0.0003 0.00030.0003 0.0003 P Iron oxide (yellow) 0.006 0.006 0.006 0.006 W WaterBalance Balance Balance Balance High temperature stability ◯ X X ΔEmulsified particle size ◯ X X Δ Low temperature stability ◯ — — — pH7.4 — — — Sensation during use (stickiness) ◯ — — X Sensation during use(absorption) ◯ — — X

Table 1-1 shows the results of checking condition (A) in claim 1.

When any of ingredients A-1, A-2, and A-3 is removed (Comparativeexamples 1-1 to 1-3), the stability and usability deteriorate.

In particular, when A-1 or A-3 is removed (Comparative examples 1-1 and1-2), emulsified products that can be evaluated for the sensation duringuse are not formed to begin with.

Examples 1, 3, and 4, and Comparative examples 1-4

TABLE 1-2 Condition (B) in claim 1 Comparative Part Ingredient Example 1Example 3 Example 4 example 1-4 O A-1 PEG40 stearate 1.1 1.1 1.1 1.1 OPEG100 stearate — — — — O A-2 Sorbitan tristearate 1 1 1 1 O A-3 Selfemulsified glyceryl stearate 2.5 2.5 2.5 2.5 O BTert-butylmethoxybenzoylmethane 2 1 2 3 O Bis ethylhexyloxyphenolmethoxyphenyl triazine 0.5 0.5 2 3 O C Octocrylene 5 5 5 5 O Ethylhexylmethoxycinnamate — — — — W D Phenylbenzimidazolesulfonic acid 2 2 2 2 OE Stearyl alcohol 0.5 0.5 0.5 0.5 O Behenyl alcohol 2 2 2 2 O Cetanol —— — — O F 2-ethyhexyl 2-ethylhexanoate — — — — O Isononyl isononanoate —— — — W G PEG/PPG-14/7 dimethyl ether — — — — W PEG/PPG-17/4 dimethylether — — — — W H Carnosine — — — — W Other Glycerin 7 7 7 7 WDipropylene glycol 5 5 5 5 W Butylene glycol 8 8 8 8 W Xanthan gum 0.150.15 0.15 0.15 O Myristyl myristate 2 2 2 2 O Microcrystalline wax 1 1 11 O Dimeticone 3 4 3 3 O Squalane 5 5 3.5 1.5 W Triethanolamine 1.2 1.21.2 1.2 P Titanium oxide 1 1 1 1 P Spherical cellulose 0.5 0.5 0.5 0.5 WEdetate 0.1 0.1 0.1 0.1 W Phenoxy ethanol 0.5 0.5 0.5 0.5 W Sodiumpyrosulfite 0.003 0.003 0.003 0.003 W Hexametaphosphoric soda 0.1 0.10.1 0.1 P Iron oxide (red) 0.0003 0.0003 0.0003 0.0003 P Iron oxide(yellow) 0.006 0.006 0.006 0.006 W Water Balance Balance Balance BalanceHigh temperature stability ◯ ◯ ◯ ◯ Emulsified particle size ◯ ◯ ◯ ◯ Lowtemperature stability ◯ ◯ ◯ X pH 7.4 7.4 7.4 7.4 Sensation during use(Stickiness) ◯ ◯ ◯ ◯ Sensation during use (absorption) ◯ ◯ ◯ ◯

Table 1-2 shows the results of checking condition (B) in claim 1.

The low temperature stability deteriorates when the amount of theingredients used in (B) is increased (Comparative example 1-4).

Examples 1, 2, 5, and 6 and Comparative examples 1-5 to 1-6

TABLE 1-3 Condition (C) in claim 1 Comparative Comparative PartIngredient Example 1 Example 2 Example 5 Example 6 example 1-5 example1-6 O A-1 PEG40 stearate 1.1 — 1.1 1.1 1.1 1.1 O PEG100 stearate — 1 — —— — O A-2 Sorbitan tristearate 1 1.1 1 1 1 1 O A-3 Self emulsifiedglyceryl stearate 2.5 2.5 2.5 2.5 2.5 2.5 O BTert-butylmethoxybenzoylmethane 2 2 2 2 2 1 O Bis ethylhexyloxyphenolmethoxyphenyl 0.5 0.5 0.5 0.5 0.5 0.5 triazine O C Octocrylene 5 3 2 5 —5 O Ethylhexyl methoxycinnamate — 5 1 5 — 10 W DPhenylbenzimidazolesulfonic acid 2 2 2 2 2 2 O E Stearyl alcohol 0.5 10.5 0.5 0.5 0.5 O Behenyl alcohol 2 0.5 2 2 2 2 O Cetanol — 1 — — — — OF 2-ethyhexyl 2-ethylhexanoate — — — — — — O Isononyl isononanoate — — —— — — W G PEG/PPG-14/7 dimethyl ether — — — — — — W PEG/PPG-17/4dimethyl ether — — — — — — W H Carnosine — — — — — — W Other Glycerin 77 7 7 7 7 W Dipropylene glycol 5 5 5 5 5 5 W Butylene glycol 8 8 8 8 8 8W Xanthan gum 0.15 0.15 0.15 0.15 0.15 0.15 O Myristyl myristate 2 2 2 22 1 O Microcrystalline wax 1 1 1 1 1 1 O Dimeticone 3 3 5 2 7 — OSqualane 5 2 5 1 6 — W Triethanolamine 1.2 1.2 1.2 1.2 1.2 1.2 PTitanium oxide 1 1 1 1 1 1 P Spherical cellulose 0.5 0.5 0.5 0.5 0.5 0.5W Edetate 0.1 0.1 0.1 0.1 0.1 0.1 W Phenoxy ethanol 0.5 0.5 0.5 0.5 0.50.5 W Sodium pyrosulfite 0.003 0.003 0.003 0.003 0.003 0.003 WHexametaphosphoric soda 0.1 0.1 0.1 0.1 0.1 0.1 P Iron oxide (red)0.0003 0.0003 0.0003 0.0003 0.0003 0.0003 P Iron oxide (yellow) 0.0060.006 0.006 0.006 0.006 0.006 W Water Balance Balance Balance BalanceBalance Balance High temperature stability ◯ ◯ ◯ ◯ ◯ X Emulsifiedparticle size ◯ ◯ ◯ ◯ ◯ ◯ Low temperature stability ◯ ◯ ◯ ◯ X ◯ pH 7.47.4 7.4 7.4 7.4 7.4 Sensation during use (stickiness) ◯ ◯ ◯ ◯ ⊚ XSensation during use (absorption) ◯ ◯ ◯ ◯ ◯ ◯

Table 1-3 shows the results of checking condition (C) in claim 1.

The low temperature stability deteriorates when the amount of theingredients used in (C) is decreased (removed in Comparative example1-5). The high temperature stability deteriorates when the amount isincreased (Comparative example 1-6).

Examples 1, 7, and 8 and Comparative examples 1-7 to 1-8

TABLE 1-4 Condition (D) in claim 1 Comparative Comparative PartIngredient Example 1 Example 7 Example 8 example 1-7 example 1-8 O A-1PEG40 stearate 1.1 1.1 1.1 1.1 1.1 O PEG100 stearate — — — — — O A-2Sorbitan tristearate 1 1 1 1 1 O A-3 Self emulsified glyceryl stearate2.5 2.5 2.5 2.5 2.5 O B Tert-butylmethoxybenzoylmethane 2 2 2 2 2 O Bisethylhexyloxyphenol methoxyphenyl triazine 0.5 0.5 0.5 0.5 0.5 O COctocrylene 5 5 5 5 5 O Ethylhexyl methoxycinnamate — — — — — W DPhenylbenzimidazolesulfonic acid 2 1 3 0.01 6 O E Stearyl alcohol 0.50.5 0.5 0.5 0.5 O Behenyl alcohol 2 2 2 2 2 O Cetanol — — — — — O F2-ethyhexyl 2-ethylhexanoate — — — — — O Isononyl isononanoate — — — — —W G PEG/PPG-14/7 dimethyl ether — — — — — W PEG/PPG-17/4 dimethyl ether— — — — — W H Carnosine — — — — — W Other Glycerin 7 7 7 7 7 WDipropylene glycol 5 5 5 5 5 W Butylene glycol 8 8 8 8 8 W Xanthan gum0.15 0.15 0.15 0.15 0.15 O Myristyl myristate 2 2 2 2 2 OMicrocrystalline wax 1 1 1 1 1 O Dimeticone 3 3 3 3 3 O Squalane 5 5 5 55 W Triethanolamine 1.2 0.6 1.8 0.006 3.6 P Titanium oxide 1 1 1 1 1 PSpherical cellulose 0.5 0.5 0.5 0.5 0.5 W Edetate 0.1 0.1 0.1 0.1 0.1 WPhenoxy ethanol 0.5 0.5 0.5 0.5 0.5 W Sodium pyrosulfite 0.003 0.0030.003 0.003 0.003 W Hexametaphosphoric soda 0.1 0.1 0.1 0.1 0.1 P Ironoxide (red) 0.0003 0.0003 0.0003 0.0003 0.0003 P Iron oxide (yellow)0.006 0.006 0.006 0.006 0.006 W Water Balance Balance Balance BalanceBalance High temperature stability ◯ ◯ ◯ ◯ ◯ Emulsified particle size ◯◯ ◯ Δ ◯ Low temperature stability ◯ ◯ ◯ ◯ ◯ pH 7.4 7.4 7.4 7.4 7.4Sensation during use (stickiness) ◯ ◯ ◯ ◯ Δ Sensation during use(absorption) ◯ ◯ ◯ Δ ◯

Table 1-4 shows the results of checking condition (D) in claim 1.

The low temperature stability deteriorates when the amount of theingredients used in (D) is decreased (Comparative example 1-7). Thesensation during use deteriorates when the amount is increased(Comparative example 1-8).

Examples 1, 9, and 10 and Comparative examples 2-1 to 2-2

TABLE 2-1 Condition (A) in claim 1 Comparative Comparative PartIngredient Example 1 example 2-1 Example 9 Example 10 example 2-2 O A-1PEG40 stearate 1.1 0.11 0.44 1.32 1.54 O A-2 Sorbitan tristearate 1 0.10.4 1.2 1.4 O A-3 Self emulsified glyceryl stearate 2.5 0.25 1 3 3.5 O BTert-butylmethoxybenzoylmethane 2 2 2 2 2 O Bis ethylhexyloxyphenolmethoxyphenyl triazine 0.5 0.5 0.5 0.5 0.5 O C Octocrylene 5 5 5 5 5 OEthylhexyl methoxycinnamate — — — — — W D Phenylbenzimidazolesulfonicacid 2 2 2 2 2 O E Stearyl alcohol 0.5 0.5 0.5 0.5 0.5 O Behenyl alcohol2 2 2 2 2 O Cetanol — — — — — O F 2-ethyhexyl 2-ethylhexanoate — — — — —O Isononyl isononanoate — — — — — W G PEG/PPG-14/7 dimethyl ether — — —— — W PEG/PPG-17/4 dimethyl ether — — — — — W H Carnosine — — — — — WOther Glycerin 7 7 7 7 7 W Dipropylene glycol 5 5 5 5 5 W Butyleneglycol 8 8 8 8 8 W Xanthan gum 0.15 0.15 0.15 0.15 0.15 O Myristylmyristate 2 2 2 2 2 O Microcrystalline wax 1 1 1 1 1 O Dimeticone 3 3 33 3 O Squalane 5 5 5 5 5 W Triethanolamine 1.2 1.2 1.2 1.2 1.2 PTitanium oxide 1 1 1 1 1 P Spherical cellulose 0.5 0.5 0.5 0.5 0.5 WEdetate 0.1 0.1 0.1 0.1 0.1 W Phenoxy ethanol 0.5 0.5 0.5 0.5 0.5 WSodium pyrosulfite 0.003 0.003 0.003 0.003 0.003 W Hexametaphosphoricsoda 0.1 0.1 0.1 0.1 0.1 P Iron oxide (red) 0.0003 0.0003 0.0003 0.00030.0003 P Iron oxide (yellow) 0.006 0.006 0.006 0.006 0.006 W WaterBalance Balance Balance Balance Balance Condition (A-1) + (A-2) + (A-3)4.6 0.46 1.84 5.52 6.44 in claim 2 (A-3)/(A-1) + (A-2) + (A-3) 0.54350.5435 0.5435 0.5435 0.5435 E/(A-1) + (A-2) + (A-3) 0.5435 5.4348 1.35870.4529 0.3882 High temperature stability ◯ X ◯ ⊚ ⊚ Cycling stability ◯ —— — — Sensation during use (stickiness) ◯ ⊚ ◯ ◯ Δ Sensation during use(absorption) ◯ ◯ ◯ ◯ ◯

Table 2-1 shows the results of checking for the total of A-1 to A-3 inclaim 1.

When the total of these ingredients decreases, the high temperaturestability deteriorates (Comparative example 2-1). The sensation duringuse deteriorates when the amount is increased (Comparative example 2-2).

Examples 1 and 11, and Comparative examples 2-3 to 2-4

TABLE 2-2 Condition (1) in claim 2 Comparative Comparative PartIngredient Example 1 example 2-3 Example 11 example 2-4 O A-1 PEG40stearate 1.1 2.2 0.85 0.6 O A-2 Sorbitan tristearate 1 2 0.75 0.5 O A-3Self emulsified glyceryl stearate 2.5 0.4 3 3.5 O BTert-butylmethoxybenzoylmethane 2 2 2 2 O Bis ethylhexyloxyphenolmethoxyphenyl triazine 0.5 0.5 0.5 0.5 O C Octocrylene 5 5 5 5 OEthylhexyl methoxycinnamate — — — — W D Phenylbenzimidazolesulfonic acid2 2 2 2 O E Stearyl alcohol 0.5 0.5 0.5 0.5 O Behenyl alcohol 2 2 2 2 OCetanol — — — — O F 2-ethyhexyl 2-ethylhexanoate — — — — O Isononylisononanoate — — — — W G PEG/PPG-14/7 dimethyl ether — — — — WPEG/PPG-17/4 dimethyl ether — — — — W H Carnosine — — — — W OtherGlycerin 7 7 7 7 W Dipropylene glycol 5 5 5 5 W Butylene glycol 8 8 8 8W Xanthan gum 0.15 0.15 0.15 0.15 O Myristyl myristate 2 2 2 2 OMicrocrystalline wax 1 1 1 1 O Dimeticone 3 3 3 3 O Squalane 5 5 5 5 WTriethanolamine 1.2 1.2 1.2 1.2 P Titanium oxide 1 1 1 1 P Sphericalcellulose 0.5 0.5 0.5 0.5 W Edetate 0.1 0.1 0.1 0.1 W Phenoxy ethanol0.5 0.5 0.5 0.5 W Sodium pyrosulfite 0.003 0.003 0.003 0.003 WHexametaphosphoric soda 0.1 0.1 0.1 0.1 P Iron oxide (red): 0.00030.0003 0.0003 0.0003 P Iron oxide (yellow): 0.006 0.006 0.006 0.006 WWater Balance Balance Balance Balance Condition (A-1) + (A-2) + (A-3)4.6 4.6 4.6 4.6 in claim 2 (A-3)/(A-1) + (A-2) + (A-3) 0.5435 0.0870.6522 0.7609 E/(A-1) + (A-2) + (A-3) 0.5435 0.5435 0.5435 0.5435 Hightemperature stability ◯ Δ ◯ Δ Cycling stability ◯ Δ ◯ Δ Sensation duringuse (stickiness) ◯ ◯ ◯ Δ Sensation during use (absorption) ◯ ◯ ◯ Δ

Table 2-2 shows the results of checking condition (1) in claim 2.

When the ratio of A-3 to the total amount of A-1 to A-3 is low, thestability deteriorates (Comparative example 2-3). When this ratio ishigh, the sensation during use and stability deteriorate (Comparativeexample 2-4).

Examples 1, 12, and 13 and Comparative examples 2-5 to 2-6

TABLE 2-3 Condition (2) in claim 2 Comparative Comparative PartIngredient Example 1 example 2-5 Example 12 Example 13 example 2-6 O A-1PEG40 stearate 1.1 1.1 1.1 1.1 1.1 O A-2 Sorbitan tristearate 1 1 1 1 1O A-3 Self emulsified glyceryl stearate 2.5 2.5 2.5 2.5 2.5 O BTert-butylmethoxybenzoylmethane 2 2 2 2 2 O Bis ethylhexyloxyphenolmethoxyphenyl triazine 0.5 0.5 0.5 0.5 0.5 O C Octocrylene 5 5 5 5 5 OEthylhexyl methoxycinnamate — — — — — W D Phenylbenzimidazolesulfonicacid 2 2 2 2 2 O E Stearyl alcohol 0.5 0.15 0.3 0.6 1 O Behenyl alcohol2 1 1.5 2.4 4 O Cetanol — — — — — O F 2-ethyhexyl 2-ethylhexanoate — — —— — O Isononyl isononanoate — — — — — W G PEG/PPG-14/7 dimethyl ether —— — — — W PEG/PPG-17/4 dimethyl ether — — — — — W H Carnosine — — — — —W Other Glycerin 7 7 7 7 7 W Dipropylene glycol 5 5 5 5 5 W Butyleneglycol 8 8 8 8 8 W Xanthan gum 0.15 0.15 0.15 0.15 0.15 O Myristylmyristate 2 2 2 2 2 O Microcrystalline wax 1 1 1 1 1 O Dimeticone 3 3 33 3 O Squalane 5 5 5 5 5 W Triethanolamine 1.2 1.2 1.2 1.2 1.2 PTitanium oxide 1 1 1 1 1 P Spherical cellulose 0.5 0.5 0.5 0.5 0.5 WEdetate 0.1 0.1 0.1 0.1 0.1 W Phenoxy ethanol 0.5 0.5 0.5 0.5 0.5 WSodium pyrosulfite 0.003 0.003 0.003 0.003 0.003 W Hexametaphosphoricsoda 0.1 0.1 0.1 0.1 0.1 P Iron oxide (red) 0.0003 0.0003 0.0003 0.00030.0003 P Iron oxide (yellow) 0.006 0.006 0.006 0.006 0.006 W WaterBalance Balance Balance Balance Balance Condition (A-1) + (A-2) + (A-3)4.6 4.6 4.6 4.6 4.6 in claim 2 (A-3)/(A-1) + (A-2) + (A-3) 0.5435 0.54350.5435 0.5435 0.5435 E/(A-1) + (A-2) + (A-3) 0.5435 0.25 0.3913 0.65221.087 High temperature stability ◯ X ◯ ⊚ ⊚ Cycling stability ◯ ⊚ ⊚ ◯ ΔSensation during use (stickiness) ◯ ◯ ◯ ◯ ◯ Sensation during use(absorption) ◯ ◯ ◯ ◯ Δ

Table 2-3 shows the results of checking condition (2) in claim 2.

When the ratio of ingredient E to the total amount of A-1 to A-3 is low,the stability deteriorates (Comparative example 2-5). When this ratio ishigh, the cycling stability and the sensation during use (absorption)deteriorate (Comparative example 2-6).

Example 1, Examples 14-17, and Comparative examples 3-1 to 3-2

TABLE 3-1 Conditions of claim 3 Comparative Comparative Part IngredientExample 1 example 3-1 Example 14 Example 15 Example 16 Example 17example 3-2 O A-1 PEG40 stearate 1.1 1.1 1.1 1.1 1.1 1.1 1.1 O A-2Sorbitan tristearate 1 1 1 1 1 1 1 O A-3 Self emulsified glycerylstearate 2.5 2.5 2.5 2.5 2.5 2.5 2.5 O B Tert- 2 2 2 2 2 2 1butylmethoxybenzoylmethane O Bis ethylhexyloxyphenol 0.5 0.5 0.5 0.5 0.50.5 0.5 methoxyphenyl triazine O C Octocrylene 5 5 5 5 5 5 2 OEthylhexyl methoxycinnamate — — — — — — — W DPhenylbenzimidazolesulfonic 2 2 2 2 2 2 2 acid O E Stearyl alcohol 0.50.5 0.5 0.5 0.5 0.5 0.5 O Behenyl alcohol 2 2 2 2 2 2 2 O Cetanol — — —— — — — O F 2-ethyhexyl 2-ethylhexanoate — 0.1 1 2 — 5 10 O IsononylIsononanoate — — — — 2 — — W G PEG/PPG-14/7 dimethyl ether — — — — — — —W PEG/PPG-17/4 dimethyl ether — — — — — — — W H Carnosine — — — — — — —W Other Glycerin 7 7 7 7 7 7 7 W Dipropylene glycol 5 5 5 5 5 5 5 WButylene glycol 8 8 8 8 8 8 8 W Xanthan gum 0.15 0.15 0.15 0.15 0.150.15 0.15 O Myristyl myristate 2 2 2 2 2 2 2 O Microcrystalline wax 1 11 1 1 1 1 O Dimeticone 3 3 3 3 3 3 2 O Squalane 5 4.9 4 3 3 — — WTriethanolamine 1.2 1.2 1.2 1.2 1.2 1.2 1.2 P Titanium oxide 1 1 1 1 1 11 P Spherical cellulose 0.5 0.5 0.5 0.5 0.5 0.5 0.5 W Edetate 0.1 0.10.1 0.1 0.1 0.1 0.1 W Phenoxy ethanol 0.5 0.5 0.5 0.5 0.5 0.5 0.5 WSodiun pyrosulfite 0.003 0.003 0.003 0.003 0.003 0.003 0.003 WHexametaphosphoric soda 0.1 0.1 0.1 0.1 0.1 0.1 0.1 P Iron oxide (red)0.0003 0.0003 0.0003 0.0003 0.0003 0.0003 0.0003 P Iron oxide (yellow)0.006 0.006 0.006 0.006 0.006 0.006 0.006 W Water Balance BalanceBalance Balance Balance Balance Balance High temperature stability ◯ ◯ ◯◯ ◯ ◯ Δ pH 7.4 7.4 7.4 7.4 7.4 7.4 7.4 Emulsified particle size ◯ ◯ ◯ ◯◯ ◯ ◯ Cycling stability ◯ ◯ ⊚ ⊚ ⊚ ⊚ ⊚ Sensation during use ◯ ◯ ◯ ◯ ◯ ◯ ◯(stickiness) Sensation during use ◯ ◯ ◯ ⊚ ⊚ ⊚ ⊚ (absorption)

Table 3-1 shows the results of checking condition (F) in claim 3.

The effect of the amount of ingredient F being small is the same as thatin Example 1. That is, no increase in the cycling stability or thesensation during use is achieved (Comparative example 3-1).

When there is a certain amount of ingredient F, the cycling stabilityand the sensation during use improve even more than Example 1 (Examples14-17).

On the other hand, when the amount of ingredient F is too much, the hightemperature stability deteriorates slightly (Comparative example 3-2).

Example 1, Examples 18-21, and Comparative examples 3-3 to 3-4

TABLE 3-2 Conditions of claim 4 Comparative Comparative Part IngredientExample 1 example 3-3 Example 18 Example 19 Example 20 Example 21example 3-4 O A-1 PEG40 stearate 1.1 1.1 1.1 1.1 1.1 1.1 1.1 O A-2Sorbitan tristearate 1 1 1 1 1 1 1 O A-3 Self emulsified glycerylstearate 2.5 2.5 2.5 2.5 2.5 2.5 2.5 O B Tert- 2 2 2 2 2 2 2butylmethoxybenzoylmethane O Bis ethylhexyloxyphenol 0.5 0.5 0.5 0.5 0.50.5 0.5 methoxyphenyl triazine O C Octocrylene 5 5 5 5 5 5 5 OEthylhexyl methoxycinnamate — — — — — — — W DPhenylbenzimidazolesulfonic 2 2 2 2 2 2 2 acid O E Stearyl alcohol 0.50.5 0.5 0.5 0.5 0.5 0.5 O Behenyl alcohol 2 2 2 2 2 2 2 O Cetanol — — —— — — — O F 2-ethyhexyl 2-ethylhexanoate — — — — — — — O Isononylisononanoate — — — — — — — W G PEG/PPG-14/7 dimethyl ether — 0.1 1 2 — 510 W PEG/PPG-17/4 dimethyl ether — — — — 2 — — W H Carnosine — — — — — —— W Other Glycerin 7 7 7 7 7 7 7 W Dipropylene glycol 5 5 5 5 5 5 5 WButylene glycol 8 8 8 8 8 8 8 W Xanthan gum 0.15 0.15 0.15 0.15 0.150.15 0.15 O Myristyl myristate 2 2 2 2 2 2 2 O Microcrystalline wax 1 11 1 1 1 1 O Dimeticone 3 3 3 3 3 3 3 O Squalane 5 5 5 5 5 5 5 WTriethanolamine 1.2 1.2 1.2 1.2 1.2 1.2 1.2 P Titanium oxide 1 1 1 1 1 11 P Spherical cellulose 0.5 0.5 0.5 0.5 0.5 0.5 0.5 W Edetate 0.1 0.10.1 0.1 0.1 0.1 0.1 W Phenoxy ethanol 0.5 0.5 0.5 0.5 0.5 0.5 0.5 WSodium pyrosulfite 0.003 0.003 0.003 0.003 0.003 0.003 0.003 WHexametaphosphoric soda 0.1 0.1 0.1 0.1 0.1 0.1 0.1 P Iron oxide (red):0.0003 0.0003 0.0003 0.0003 0.0003 0.0003 0.0003 P Iron oxide (yellow):0.006 0.006 0.006 0.006 0.006 0.006 0.006 W Water Balance BalanceBalance Balance Balance Balance Balance High temperature stability ◯ ◯ ◯⊚ ⊚ ◯ Δ pH 7.4 7.4 7.4 7.4 7.4 7.4 7.4 Emulsified particle size ◯ ◯ ⊚ ⊚⊚ ⊚ ⊚ Cycling stability ◯ ◯ ◯ ◯ ◯ ◯ ◯ Sensation during use ◯ ◯ ◯ ⊚ ⊚ ⊚ ⊚(stickiness) Sensation during use ◯ ◯ ◯ ⊚ ⊚ ⊚ ⊚ (absorption)

Table 3-2 shows the results of checking condition (G) in claim 4.

The effect of the amount of ingredient G being too small is the same asthat in Example 1. That is, no increase in the high temperaturestability, emulsified particle size or sensation during use is achieved(Comparative example 3-3).

No effect is achieved when the amount of ingredient G is too small(Comparative example 3-3).

When there is a certain amount of ingredient G, the cycling stabilityand the sensation during use improve (Examples 18-21).

On the other hand, when the amount of ingredient G is too much, the hightemperature stability deteriorates slightly (Comparative example 3-4).

Example 1, Examples 22-23, Comparative examples 3-5

TABLE 3-3 Conditions of claim 5 Comparative Part Ingredient Example 1Example 22 Example 23 example 3-5 O A-1 PEG40 stearate 1.1 1.1 1.1 1.1 OA-2 Sorbitan tristearate 1 1 1 1 O A-3 Self emulsified glyceryl stearate2.5 2.5 2.5 2.5 O B Tert-butylmethoxybenzoylmethane 2 2 2 2 O Bisethylhexyloxyphenol methoxyphenyl triazine 0.5 0.5 0.5 0.5 O COctocrylene 5 5 5 5 O Ethylhexyl methoxycinnamate — — — — W DPhenylbenzimidazolesulfonic acid 2 2 2 2 O E Stearyl alcohol 0.5 0.5 0.50.5 O Behenyl alcohol 2 2 2 2 O Cetanol — — — — O F 2-ethyhexyl2-ethylhexanoate — — — — O Isononyl isononanoate — — — — W GPEG/PPG-14/7 dimethyl ether — — — — W PEG/PPG-17/4 dimethyl ether — — —— W H Carnosine — 1 3 4.5 W Other Glycerin 7 7 7 7 W Dipropylene glycol5 5 5 5 W Butylene glycol 8 8 8 8 W Xanthan gum 0.15 0.15 0.15 0.15 OMyristyl myristate 2 2 2 2 O Microcrystalline wax 1 1 1 1 O Dimeticone 33 3 3 O Squalane 5 5 5 5 W Triethanolamine 1.2 1.2 1.2 1.2 P Titaniumoxide 1 1 1 1 P Spherical cellulose 0.5 0.5 0.5 0.5 W Edetate 0.1 0.10.1 0.1 W Phenoxy ethanol 0.5 0.5 0.5 0.5 W Sodium pyrosulfite 0.0030.003 0.003 0.003 W Hexametaphosphoric soda 0.1 0.1 0.1 0.1 P Iron oxide(red) 0.0003 0.0003 0.0003 0.0003 P Iron oxide (yellow) 0.006 0.0060.006 0.006 W Water Balance Balance Balance Balance High temperaturestability ◯ ◯ ◯ ◯ pH 7.4 7.4 7.6 8.3 Emulsified particle size ◯ ◯ ◯ ◯Cycling stability ◯ ◯ ◯ ◯ Sensation during use (stickiness) ◯ ◯ ◯ ◯Sensation during use (absorption) ◯ ◯ ◯ ◯

Table 3-3 shows the results of checking condition (H) in claim 5.

In the present invention, even when ingredient H is added, the pH ismaintained at the same level as in Example 1 (Examples 22 and 23).However, when the amount of ingredient H is too much, the pH exceeds 8(Comparative example 3-5).

INDUSTRIAL APPLICABILITY

The present invention can provide an oil-in-water emulsified sunscreencosmetic that is superior in ultraviolet protection as well as instability and the sensation during use. That is, a sunscreen cosmetic'sultraviolet protection can be increased and also the stability of thebase agent and the sensation during use can be improved by providing anoil-in-water emulsified sunscreen cosmetic that satisfies all of theaforementioned conditions (A), (B), (C), (D), and (E).

Also, in the present invention, even when carnosine, which is a priorart antioxidant and anti-wrinkling agent, is added, an increase in thebase agent pH due to basic dipeptide carnosine can be prevented.Therefore, a sunscreen cosmetic can stably contain carnosine whilemaintaining the stability of the base agent and the sensation duringuse.

1. An oil-in-water emulsified sunscreen cosmetic that satisfies all ofthe following conditions (A), (B), (C), (D), and (E): (A) Containing thefollowing three types of surfactants (A-1)-(A-3) in the amount of 1-6 wt% of the total amount of the cosmetic: (A-1) A POE stearic ester havinga POE mole number of 20-120 (A-2) Sorbitan tristearate (A-3) Glycerylstearate having a HLB of 5-8; (B) Containing the following oil solubleultraviolet absorbent, which is solid at room temperature, in the amountof 0.01-5 wt % of the total amount of the cosmetic:Bis-ethylhexyloxyphenolmethoxyphenyltriazine and/ortert-butylmethoxybenzoylmethane; (C) Containing the following oilsoluble ultraviolet absorbent, which is liquid at room temperature, inthe amount of 1-14 wt % of the total amount of the cosmetic: Ethylhexylmethoxycinnamate and/or octocrylene; (D) Containing the following watersoluble ultraviolet absorbent in the amount of 0.1-5 wt % of the totalamount of the cosmetic: Phenylbenzimidazolesulfonic acid; and (E)Containing higher alcohol having 14-24 carbon atoms.
 2. The oil-in-wateremulsified sunscreen cosmetic of claim 1 that further satisfies thefollowing conditions (1) and (2): (1) The ingredient (A-3) content is 10wt %-75 wt % of the total amount of ingredients (A-1), (A-2), and (A-3);and (2) The ingredient (E) content is 30-90 wt % of the total amount ofingredients (A-1), (A-2), and (A-3).
 3. The oil-in-water emulsifiedsunscreen cosmetic of claim 1, further comprising: (F) mono-ester oilrepresented by the following formula (1) in the amount of 0.2-9 wt % ofthe total amount of the cosmetic:[Chemical formula 1]R₁COOR₂  (1) (In this formula, R₁ denotes an alkyl group having 5-11carbon atoms, and R₂ denotes an alkyl group having 3-11 carbon atoms.)4. The oil-in-water emulsified sunscreen cosmetic of claim 1, furthercomprising: (G) a random copolymer ether compound of ethylene glycol andpropylene glycol represented by the following formula (2) in the amountof 0.2-9 wt % of the total amount of the cosmetic:[Chemical formula 2]RO-[(EO)_(m)(AO)_(n)]-OR  (2) (In this formula, AO denotes anoxyalkylene group having 3-4 carbon atoms, EO denotes an oxyethylenegroup, m and n, respectively, are average addition mole numbers of saidoxyalkylene group and oxyethylene group; also 1=<m=<70 and 1=<n=<70; theratio of the oxyethylene group to the total of the oxyalkylene grouphaving 3-4 carbon atoms and the oxyethylene group is 50-100 wt %; theoxyalkylene group having 3-4 carbon atoms and the oxyethylene group arerandomly added; R denotes a hydrocarbon group having 1-4 atoms orhydrogen atom, each different or identical, and the ratio of the numberof hydrogen atoms to the number of the hydrocarbon groups is 0.15 orless.)
 5. The oil-in-water emulsified sunscreen cosmetic of claim 1,further comprising: (H) β-alanyl-L-histidine and/or its salt in theamount of 0.1-4 wt % of the total amount of the cosmetic and cosmetic'spH being less than
 8. 6. The oil-in-water emulsified sunscreen cosmeticof claim 2, further comprising: (F) mono-ester oil represented by thefollowing formula (1) in the amount of 0.2-9 wt % of the total amount ofthe cosmetic:[Chemical formula 1]R₁COOR₂  (1) (In this formula, R₁ denotes an alkyl group having 5-11carbon atoms, and R₂ denotes an alkyl group having 3-11 carbon atoms).7. The oil-in-water emulsified sunscreen cosmetic of claim 2, furthercomprising: (G) a random copolymer ether compound of ethylene glycol andpropylene glycol represented by the following formula (2) in the amountof 0.2-9 wt % of the total amount of the cosmetic:[Chemical formula 2]RO-[(EO)_(m)(AO)_(n)]-OR  (2) (in this formula, AO denotes anoxyalkylene group having 3-4 carbon atoms, EO denotes an oxyethylenegroup, m and n, respectively, are average addition mole numbers of saidoxyalkylene group and oxyethylene group; also 1=<m=<70 and 1=<n=<70; theratio of the oxyethylene group to the total of the oxyalkylene grouphaving 3-4 carbon atoms and the oxyethylene group is 50-100 wt %; theoxyalkylene group having 3-4 carbon atoms and the oxyethylene group arerandomly added; R denotes a hydrocarbon group having 1-4 atoms orhydrogen atom, each different or identical, and the ratio of the numberof hydrogen atoms to the number of the hydrocarbon groups is 0.15 orless).
 8. The oil-in-water emulsified sunscreen cosmetic of claim 3,further comprising: (G) a random copolymer ether compound of ethyleneglycol and propylene glycol represented by the following formula (2) inthe amount of 0.2-9 wt % of the total amount of the cosmetic:[Chemical formula 2]RO-[(EO)_(m)(AO)_(n)]-OR  (2) (in this formula, AO denotes anoxyalkylene group having 3-4 carbon atoms, EO denotes an oxyethylenegroup, m and n, respectively, are average addition mole numbers of saidoxyalkylene group and oxyethylene group; also 1=<m=<70 and 1=<n=<70; theratio of the oxyethylene group to the total of the oxyalkylene grouphaving 3-4 carbon atoms and the oxyethylene group is 50-100 wt %; theoxyalkylene group having 3-4 carbon atoms and the oxyethylene group arerandomly added; R denotes a hydrocarbon group having 1-4 atoms orhydrogen atom, each different or identical, and the ratio of the numberof hydrogen atoms to the number of the hydrocarbon groups is 0.15 orless).
 9. The oil-in-water emulsified sunscreen cosmetic of claim 2,further comprising: (H) β-alanyl-L-histidine and/or its salt in theamount of 0.1-4 wt % of the total amount of the cosmetic and cosmetic'spH being less than
 8. 10. The oil-in-water emulsified sunscreen cosmeticof claim 3, further comprising: (H) β-alanyl-L-histidine and/or its saltin the amount of 0.1-4 wt % of the total amount of the cosmetic andcosmetic's pH being less than
 8. 11. The oil-in-water emulsifiedsunscreen cosmetic of claim 4, further comprising: (H)β-alanyl-L-histidine and/or its salt in the amount of 0.1-4 wt % of thetotal amount of the cosmetic and cosmetic's pH being less than 8.